Process for the treatment of hydrocarbons



July 9, 1946. F. E. FREY l PRocEss FOR THE `'JJREATNIEM' 4011'.l-I'unmocARoNs Filed July 11, 1942 n moisture.

Patented July 9, 1,946

. uNflsTEofl-STATES PATENT: j

, 2,403,714- PROCESS FOR'rHE TitlgnjllyiENT'oir'-Y Y `HYDROCAR-BONSy I Delaware' Applieationculy 11, l1942-,"l

Y 1a claims.vv (ol. Q01- 1683.49

This' invention relates' ,tothe treatment; Of by: drocarbonmaterials.l More particularly it V,ree

lates-:to the conversion, vley-'an alkylation reaction in the presence of a iiuorine-containing catalyst, of relatively lowl-vboilingvv Yhydrocarbons to motor fuel hydrocarbons.` Still morefparticularly, it relates to the removal of organically combined fluolrine from the product vof such'fconversion. This` application is acontinuation-in-part of my` copendingapplication,,Serial No. 398,361A,vled June 16,.1941, now U. S. Patent 2,3l7,945,issued May 2,1944-i f y In'the manufacture; of rhydrocarbons by processes in whichViiuorine-containinglcatalysts are used, small proportions of organic'fluorine-.containing byfproductsare formed.V t These vprocesses may involve reactionsisuch aspolymerzation and alkylation of relatively low-boilinghydrocarbons to produce motor-fuelhydrocarbonsin the presencerof catalysts lcomprising one or more of such iluorinacompoundsI asfh'ydrofluoric acid, boronY caftio'nf inla 4process for Frederick E. Frey,Bartlesville;l kla.; assigner-ato:l 3 Phillips VPetroleum Company, a= corporation of, l ,Y K

varial No; teaser *boiling alkylatableY hydrocarbons in tlfie'presence of uorin'e. compounds;` a selected'ipartl or`r all bof' the hydrocarbon. effluent from ranalky'latin'g 'zone may: be f advantageously ysubjected tothegaction of. a s'olid porouscontact: material `toirernove.o'rV- ganic luorine'coinpounds.

Y An'lobject'of this invention isito efectsubstantiallyfcomplete removal of .'uorine; fromuhydro-f carbonliuids' containing organic fluorine .come pounds. asvr impurities.`

Al further: :object :of thisinvention is ank imi l proved'lpr'ocesssforobtaining. a substantially fluo rime-free Aa'lkylate from" the' alkylationi of hydro# Vcarbons .in the presence-tof al catalyst coxm'irlsingV Y ,y a iluori'ne compound.

trifluoride, and the like. Although the exactna-r ture or composition of. the organic fluorine-containing by-products which may bekvformed has not been dentely establishedythey are believed tobepredominantly alkyl and/tor aryl. fluorides. They are not .completely removed by vwashing the hydrocarbons with alkali solutions, They tend to decompose Yat eleva'taiV temperatures; 'suon as those employed in fractional distilaticncf' the' hydrocarbons, rtherebyj'forming"hydrofluoric acid, Whichis corrosive",Y especially :in the Ypresenceof thatlare obvious.` 'f Y According toy the* aforementioned co-pendin'g application,V organic uorine compounds'may be removedv 'from hydrocarbonmaterials containing them by 'contacting' such hydrocarbonniaterials withj solid porous Contactk materials. Contactmaterials which have been found-suitableginclude `other objentsfand advantagfsfwiu .begabnarent fromy ythe followingfdescrptionitne accompanying Y ingviractions;y ,Althoughiti is possible bythe 'Inggases theyima'y thus'fcause'corro- Y sionof handlingequipment; inliquid motorffuel hydrocarbonsthey areV undesirable forreasons l.

- to` treat; the xalkylationeiiluent under such .condif A those vknown to. be catalytically active for hydron genaton or dehydrogenationreactions, such as alumina gel, activated aluminagidehydrated bauxite, chromium oxide,rrnixturesy ofialumina` and chromium. oXide,metals-"of the iron group,es peci'ally nely divided` nickel deposited onr an' in@ process of the-aforementioned c'opending applica tion to remove substantially'all'lfluorine in asin# gle treatment by- .fusing suili'centlydrastic oper. ating conditions;-.I have found it is 4advantageous tions thatrtheloiv-boilingxorganic fluorine'. is' re-r` moved, then tosep'arate from the eiluent at leastv one; relatively high-boiling fraction'yandnally .to treat this relatively highboiling fraction tome-f rnove'the high-boiling:organic-fluorine. Thereby the .most advantageousconditions for the removal of each type of organic uorinezcan .be usedr-andV equipment of' a givenA size or capacity can'beuti' lizedto the fullestadvantage.:

Y Understandingcofamyinvention maybe aided y c by reference ltothe;accompany-ingdrawing; whichA erh-support, andtlielikegl Such'contact materialsfappear to adsorb preferentially the organic fluorine compounds;y althoughthe exact mecha-- nismilnvolved is not ful-ly known.atapi'esegui'.Y.n The hydrocarbon material: being 'treated'.may. be. in".

eitherfthe liquid ort'the.:vapor1phase. Also,. ac, cordingrto theaforementionedcof-pending appli-1` isf a schematic ilowediagram Yof one arrangementl of apparatus-for practicingthe inventionl; Y Y

Analkylatable hydrocarbon and an'alkylating agent,A for example an -.isoparafn such as isobu= tane or isopentanerandian olensuch as propyl'- f ene or one orgmorejlof; the butylenes, respectively,`

Vai:efadmitted-preferablythrough a number of inalkyiating,elativelylmwf Y 3 lets, such as that represented by inlet I0, and/or through conduit II and pump I2 to alkylator I3, in which' they are agitated under alkylating conditions with concentrated or substantially anhydrous hydrofluoric acid, which may be admitted through inlet I4 and/or conduit I5 and pump I6. In the feeds to alkylator I3 the mol ratio of isoparainto olefin, or other alkylating agent, such as the corresponding alcohol or halide or the like, preferably having three to five carbon atoms in the alkyl group, is preferably in the range of 2:,1 to 20:1 or more, and the Weight ratio of hydrouoric acid to total hydrocarbons is preferably in the range of about 0.211 toj`4:1.v The feed, or at least the portion of the feed which 'contains the alkylating agent, is preferably introduced into th'e reaction mixture under conditionsfofhigh turbulence and/or in multipointwise fashion, so that the alkylating agent is rapidly mixed 'and reacted with the isobutane or other alkylatable hydrocarbon'.- Thisv procedure is advantageous. in orderto: favor the. desired .olefin-isoparaflin j unctures, or alkylation reactions, and to hinder undesirable olefin-olefin junctures,. or polymerization reactions. Preferred'operating conditions in alkylator I3,v as vfor example `for alkylating isobutane with butylenes, to which for the sake of `simplicity this description maybe primarily devoted, 'are a temperature in therange of 30 to l5.0.F., a pressure suicient to maintain all components in the liquid phase, and a contacttime or time of residence in the alkylator. of about l to 30 or more minutes; however, conditions outsidelof these ranges may be used Without passing beyondthe scope of this invention. The optimum alkylating conditions vary with different reactants;v 'for example,fin alkylating benzene with ethylene, ornormal butane with olens, in the presence.` of .hydroiluoric acid as a catalyst, the-preferred Vtemperature is in the :range of 200 to 350 F.

vAfter a suitable contact or reaction time, the resulting mixture passes through conduit I'I to separator I8, wherein it is separated into two liquid phases, as by cooling and/or gravitational or.`centrifugal means. The heavier or hydro fluoric acid. phase preferably is recycled', as through conduit I5, to alkylator I3; part of it may Abe withdrawn, as through valved outlet I9, and passed topurification or acid-recovery steps, not shownin the drawing.

Y The lighter. or hydrocarbon phase is passed through conduit 20.to azeotrope column 2|, in which it is'v separated vby fractional distillation into two fractions.. vThe overhead fractionconsists of an 'azeotropiemixture .of hydrogen fluorideY and low-boiling paraffin hydrocarbons, such as propane and isobutane. This fraction is passed throughconduit 22, condenser 23, and conduit 24. tosep-arator 25, wherein it is separated into 'twoliquid rphases, as by cooling and/or vgravitational or. centrifugal means. All of the lighter. or hydrocarbon phase is returned through ondu'itZGvas vreflux to azeotrope column 2l; thefheavier or hydrofluoric. acid phase may be recycled, as through conduit I5,..to. alkylatorA I3. @The :bottom fraction from.. columnr 2|, which consists of. hydrocarbons that are substantially free' from .dissolved hydrogen fluoride but that comprise organically combinedA luorine, is passed through! conduit 2I.to defluorinatorv 28. Defluorinator -28 may consist of any suitable closed chamber', containing a .dehydrogenation-'hydrogenation-type .contact mass, through which the hydrocarbons may; Abe' passed. Specific -contact masses which have been found suitable are alumina gel, activated alumina, dehydrated bauxite, chromium oxide, mixtures of alumina and chromium oxide, metals of the iron group, especially finely divided nickel deposited on an inert support, floridin, diatomaceous earth, and the like. Such contact lmaterials appear to adsorb preferentially the organic iluorine compounds, although the exact mechanism involved is not fully known, The hydrocarbon material being treated may be in either the liquid or the vapor phase; -since the volume is relatively small in the liquid phase condition, and since all the materialsinvolved in this process are easily maintained in the liquid V state under the preferred operating conditions, it is preferably treated in the liquid state. In general, theconditions of temperature and contact time in deiluorinator 28 should be Well below those which would induce deterioration or alteration of the hydrocarbon material. Temperaturesbetween about 50 and 4:00"` F. may be employed. The optimum temperature in any particular instance Will depend upon the nature of the contact mass, the nature of the material being treated, and the desired degree of removal of fluorine. The `preferred temperature, particu-- larly when bauxite is used, is approximately equal to or somewhatlower than the kettle temperature of column 2 I and is usually in the range of about to 350 F. By using such a temperature, the necessity for heating or cooling in deuorinator 28 is avoided, and the removal of iluorine, especially offthat fluorine which upon distillation of the vfluorine-containing material appears in the low-'boiling distillate fractions, such as 'the isobutane and butano fractions, is sufhciently complete that corrosion of equipment by fiuorine compounds in the hydrocarbon material is substantially Completely eliminated. While the same type of contact material may be utilized in both steps, different materials of the class described may be usedin each-defluorinating step.

At relatively high temperatures, Yvery high space velocities, such as about 2000 or 3000 volumes of vapor (or an equivalent number `of volumes of liquidrper volume of contact material .per hour, are'satisfactory; at relatively low temperatures, the space velocity should be comparatively low, such as perhaps 1 or 2 volumes of liquid per' hour. In general the optimum space velocity depends not only upon the temperature but also upon such factors as the content of fluorine, the pressure used, the desired extent of iluorine removal, and the particular Acontact material in use'. A suitable space velocity for any particular application may be readily found by trial by one skilled in the. art. v

The partially deuorinated hydrocarbon vmaterial passes from defluorinator 28 through conduit 29 to deisobutanizer 30, whereby it is separated into two fractions. The overhead fraction, which contains isobutane, may be recycled through valve 3| and conduit II tohydrocarbon inlet I0, or. 4part or all of it maybe withdrawn through valvedY outlet 32 to a kc iesiredadditional processing step, not shown, such .as a dehydrogenation step to produce olens for use in alkylator I3. If a substantial proportion of. 10W-.boiling material other thanv isobutane. such as propane. and lighter, is present in this fraction, preferably at least. part offitv is passed through conduit 33 ,having valvel 34 to depropanizer 35, wherefrom undesired low-boilingv material is withdrawn as an `overheadifraction. through valved outlet 36,-

" described, such as alumina, chromium oxide, etc.,

may be used in a' manner similarto 'that described above.

Because the invention may be .practiced other- Wise than as specifically described or illustrated nherein,` and because many modications and variationswithin the spirit and scope of it will be obvious to thoseskilled. in the art, the invention should not be unduly restricted by the foregoing specification and examples, butI it should be restricted only in accordance with the appended n claims.

I claim:

1. The process of removing organically combined uorine from mixtures of normally gaseous and normally liquid hydrocarbons containing said `fluorine, which comprises subjecting such a mixture to the action of a solid, porous metal oxide catalytically active for hydrogenation and dehydrogenation reactions, at a-reaction temperature and for a time suiiicient to effect substantial removal of said nuorine from said mixture and such that extensive chemical changes in the hydrocarbons of said mixture are not effected,v separating the eilluent therefrom into a normally gaseous fraction and a normally liquid fraction, andI subjecting the normally liquid fraction to the action of: a second solid, porous metal oxide catalytically active for hydrogenation and dehydrogenation reactions, at an elevated temperature to effect further removal of fluorine from said fraction.

2. The process of claim 1 in which the solid, porous metal oxide comprises aluminum oxide.

3. The process of claim 1 in which said metal `oxide is alumina in the form of bauxite.

4. The process of claim 1 in which the temperature of the rst vcontacting step is in the range of about 150 to 350 F., and the temperature in the second contacting step is higher than tha'tof 'said first contacting step and is in the range of about 200 to 400 F. Y

5. The process for producing normally liquid, highly branched, saturated-type hydrocarbons which comprises subjecting a low-boiling alkylyatable paraffin hydrocarbon to the action of an alkylating agent selected from the group which consists of olens, alcohols, and alkyl halides Vhaving three to ve carbon atoms per molecule, in the presence of substantially anhydrous hydrofluoric acid as a catalyst in an alkylation zone under alkylating conditions, separating the eiluent from said alkylation zone into a hydrofluoric acid phase and a hydrocarbon phase, `returning atv least part of the acid phase to ther alkylation zone, passing the hydrocarbon phase to av fractionation step for removing free hydrogen fluoride, passing the hydrogen fluoride-free hydrocarbon material to a first defluorinating zone containing a solid, porous metal oxide catalytically active for hydrogenation and dehydrogenation reactions, for the removal of a substantial proportion of organically combined fluorine therefrom, debutanizing the eiuent from said first defluorinating zone, and passing the remaining hydrocarbons .to a second defluorinating zone containing a solid, porous metal oxide-catalytically active for hydrogenation and dehydrogenation reactions, for the further removal of organically combined'fluorine from said fraction. Y

6. The process of claim .f5 in which the second defiuorinating zone is at a higher temperature thanthe rst.

, 7. The process of claim 5 wherein said metal oxide isalumina in theform of bauxite and in which the temperature in the iirst deiluorinatying zoneis between about 150 and 350 F. and

in the second defluorinating zone isfhigher than the temperature in said iirst deuorinating zone and is between about 200 and 400 F.

f 8.: Ak process for producing normally liquid hydrocarbons substantially free from fiuorine-containing compoundsVwhich comprises alkylating a low-boiling alkylatable hydrocarbonwith `an alkylation agent in an alkylation zone in the Apresence of va Aconcentrated hydrouoric acid alkylation catalyst, removingfromeiliuents of said alkylation zone a liquid.y hydrocarbon material containing hydrouoric acid in solution, passing said liquid hydrocarbon material to a fractional distillation zone, fractionally distilling said material in said zone at a kettle temperature between about 150 and 350 F. to remove hydrofluoric acid as a low-boiling fraction, passing as a high-boiling kettle product of said distillation zone an essentially hydroluoric acid-free uorine-containing hydrocarbon mixture to a rst defluorinating zone without-substantially cooling or heating saidfraction and contacting same, at about the kettle temperature used in said distillation zone, withla solidvp orous metal oxide .cat-

alytically active for hydrogenation Vand dehydrogenation reactionsk for `altime such that extensive chemical changes in the hydrocarbons present in said mixture are 'not effected and such as to effect a substantial removal of fluorine from said mixture, passing eiiiuents of said first defluorinating zone to .a separating means, separating a low-boiling hydrocarbon fraction comprising an unreacted lalkylatable hydrocarbon, separating further a higher-boiling hydrocarbon fraction containing hydrocarbons produced by-said alkylation, passing the last said fraction to a second defluorinating zone and contacting same therein at a `temperature between about 200 and ,400 F. and higher than that used in saidV first defluorinating zonewith asolid, porous metal oxide catalytically active for hydrogenation and dehydrogenation reactions for a time Sufcient to eilectl no substantial chemical conversion of the hydrocarbons present and such that the total eiiluent from said `treatment is essentially fluorine-free, and recovering from said second defluorinating zone a uorine-free hydrocarbon alkylate so produced.

9. In a process for producing normally liquid hydrocarbons substantially free Yfrom fluorinecontaining compounds by alkylation of a low-boiling alkylatable hydrocarbon in the presence of Ya concentrated hydrofluoric acid ,alkylation catalyst, the improvement which comprises passing a liquid hydrocarbon material, separated from eflluents ofsuch an 'alkylation zone and containing hydrofluoric acid in solution, to a fractionalV distillation zone, `removing vfrom said material in saidzone hydrofluoric acid as a low-.boiling fraction, Yand passing from said distillation zone as tially heating or coolingsaid high-'boiling frac- I tion and contacting same, at about the kettle effected and such as to effect a substantial re-v moval of iiuorine from said mixture.

10. A process forproducing normally liquid hydrocarbons substantially free fromV iiuorine-containing compounds, which comprises alkylating a 10W-boiling alkylatable hydrocarbon with an alkylation agent in an alkylation zone in 'the presence of a concentrated hydroiiuoric acid alkylation catalyst, removing from etliuents of said alkylation zone a liquid hydrocarbon material containing hydroiiuoric acid in solution, passing said liquid hydrocarbon material to a fractional distillation zone, fractionally distillingsaid material in said zone at a kettle temperature between about 150 and 350 F. to remove hydrouoric acid as a low-boiling fraction, passing as a high-boiling kettle product of said distillation zone an essentially hydrofluoric acid-free fluorine-co'ntaining hydrocarbon mixture to a ydefluorinating zone without substantially cooling or heating said f fraction and contacting same, at about kettle temperature used in said distillation zone, with a solid, porous metal oxide catalytically active for hydrogenation and dehydrogenation reactions for a time such that extensive chemical changes in the hydrocarbons present in said mixture are not effected and such as to eiect a substantial removal of uorine from said mixture.

11. The process of claim 8 in which bauxite is the solid,l porous material used in each said deiiuorinating zone.

12. A process for producing normally liquid paraiiin hydrocarbons substantially free from iiuorine-containing compounds. which comprises alkylating isobutane with an olefln in an alkylation zone in the presence of a concentrated hydroiiuoric acid alkylation catalyst, removing from eiiiuents of said alkylation zone a, liquid hydrocarbon material containing hydrotluoric acid in solution, passing said liquid hydrocarbon material to a iirst fractional distillation zone and therein fractionally distilling said material at a kettle temperature not greater than about 350 F. to remove hydrofluoric acid in a low-boiling overhead fraction, passing as a high-boiling kettle product of. said distillation zone an essentially hydrofluoric acid-free iluminecontaining hydrocarbon mixture to a first deiiuorinating zone without substantially cooling or heating said fraction and contacting same, at about the kettle temperature used in said distillation zone, with a solid porous contact mass comprising alumina for a time such that extensive chemical changes in the hydrocarbons present in said mixture are not effected and such as to effect a substantial re-` moval of tluorine from said mixture, passing efiluents of said first defluorinating zone to a second, fractional distillation zone, -fractionally distilling said material in said second zone at a kettle temperature not greater than about 400 F. and higher than that used in Asaid rst distillation zone to remove low-boiling paraiiins leaving sion of the hydrocarbons present and such that the total effluent from said treatment is substantially tluorine-free, and recovering from said second deiiuorinating zone a substantially uorinefree paramnic hydrocarbon alkylate so produced.

13. The process or claim 12 in whichsaid contact masses comprise bauxite.

14. The process of claim 9 in which said solid, porous metal oxide comprises aluminum oxide.

15. The process of claim 10 in which said solid, porous metal oxide comprises aluminum oxide.

16. The process of claim 9 in which said metal oxide is alumina in the form of bauxite.

17. The process of claim 10 in which said metal oxide is alumina in the form of bauxite.

18. The process of claim 5 in which said metal oxide y in each of said defiuorinating zones is aluminum oxide and in which the temperature in the rst deiluorinating zone is between about and 350 F. and in the vsecond deiluorinating zone is higher than the temperature in said rst defluorinating zone and is between about 200 and` 19. The process of claim 8 in whichsaid metal oxide in each of said defluorlnatingl zones comprises aluminum oxide.

FREDERICK E. FREY. 

